Fuel 90 (2011) 2182–2197

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Fuel
journal homepage: www.elsevier.com/locate/fuel

TGA and macro-TGA characterisation of biomass fuels and fuel mixtures

A. Skreiberg, Ø. Skreiberg ⇑, J. Sandquist, L. Sørum
SINTEF Energy Research, Postboks 4761 Sluppen, NO-7465 Trondheim, Norway

a r t i c l e i n f o a b s t r a c t

Article history: The thermal behaviour of selected biomass fuels and mixtures as wood, demolition wood, coffee waste
Received 7 August 2010 and glossy paper was investigated using a thermogravimetric analyzer (TGA) and a macro-thermobalance
Received in revised form 10 December 2010 (macro-TGA). A kinetic model, involving first-order independent parallel reactions, was applied to results
Accepted 3 February 2011
obtained from pyrolysis TGA experiments. The pyrolysis rate was considered as the sum of the main bio-
Available online 17 February 2011
mass pseudo-components, namely cellulose, hemicellulose and lignin. Additionally, the thermal behav-
iour of the same fuels was investigated at combustion conditions in the TGA, including ignition
Keywords:
behaviour. The thermogravimetric analysis showed that each single fuel had pyrolysis and combustion
Fuel mixtures
TGA
characteristics based on its own main pseudo-components (hemicellulose, cellulose and lignin). The
Macro-TGA pyrolysis and combustion characteristics of selected fuel mixtures and the gas composition analysis from
Kinetics macro-TGA experiments showed respectively quantitative and qualitative summative behaviour based
Gas composition on the single fuels.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction
With the concern of environmental protection, the energetic
recovery of biomass via pyrolysis, gasification or combustion has
attracted increasing worldwide interest. Besides as single biomass
fuels, it is also considered an option to utilise biomass fuel mix-
tures, for different reasons, e.g. for high temperature corrosion
reduction [1–3]. The biomass combustion process can be schemat-
ically described by the diagram illustrated in Fig. 1.
The heating, drying and thermal decomposition of biomass fuels
are endothermic processes and the char and volatiles oxidation are
exothermic processes. During heating drying occurs. After drying
thermal decomposition, with significant weight loss, will take
place. The main pyrolysis products will be char with ash content,
heavy volatiles (tar) and low molecular weight gases. Carbon
monoxide and carbon dioxide will also be formed in considerable
quantities. For complete combustion, the main products are ash,
emissions (e.g. NOx and SO2) and final gaseous products as carbon
dioxide and steam. The application of technologies using biomass
fuels for energy purposes requires knowledge of the thermal
behaviour of these fuels and reliable kinetic data describing their
thermal decomposition behaviour. Thermogravimetric analysis
(TGA) is one of the most common techniques used to investigate
the thermal behaviour of small fuel samples, with no limitations
in heat and mass transfer at low heating rates. Obtained results
can be used to determine reactivity, including pyrolysis rate (mass
⇑ Corresponding author. Tel.: +47 735 93993; fax: +47 735 92889.
E-mail address: oyvind.skreiberg@sintef.no (Ø. Skreiberg).
loss per time unit) and mass loss kinetics, of the fuels. The behav-
iour of fuels when also considering limitations in heat and mass
transfer (larger particles) can be studied by macro-thermobalance
(macro-TGA) [4,5]. The aims of this paper were to evaluate the
thermal behaviour of single biomass fuels in comparison with se-
lected fuel mixtures thereof under inert and oxidising atmosphere
by carrying out TGA experiments and to study how biomass fuels
might behave in commercial plants using a macro-TGA. The DTG
curves from TGA and macro-TGA experiments with the fuels were
determined by analytical differentiation of smoothing splines, as
described in [6]. Software developed by Varhegyi was used for
determination of DTG curves and kinetic calculations assuming a
model of first-order independent parallel reactions. The obtained
results and the evaluation of the fuels’ thermal behaviour under in-
ert and oxidising atmosphere are useful, through increased funda-
mental understanding, in the development of biomass fuels
utilisation for heat and power production with low concentrations
of emissions.
2. Experimental
2.1. Biomass samples
Samples of biomass fuels, namely wood (W), demolition wood
(DW), coffee waste (CW) and glossy paper (GP), were studied using
a thermobalance Mettler Toledo TGA/SDTA 8951E. Wood pellets
were bought in commercial bags, demolition wood was received
as chips, coffee waste as briquettes (the CW used in this study is
collected during green coffee roasting and was evaluated to

0016-2361/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2011.02.012
 A. Skreiberg et al. / Fuel 90 (2011) 2182–2197 2183

Moisture (H2O) Volatiles Pyrolysis Combustion

Tar Ash
CharTar
+ Ash Final gaseous
Biomass fuel Heating and drying Thermal decomposition Gaseous
Char +products
Ash or products
Gaseous phase Emissions

Char + Ash

Fig. 1. Schematic illustration of the biomass combustion process.

Table 1
Moisture content and proximate and ultimate analysis of the fuels.

Fuel HHV (MJ/kg, db) Proximate analysis (wt.%, db) Moisture (wt.%, wb) Ultimate analysis (wt.%, dry ash free basis)
Fixed C Volatiles Ash C H O N S Cl
Wood (W) 19.95 14.34 85.58 0.08 7 50.33 6.21 43.31 0.11 0.02 0.02
Demolition wood (DW) 19.06 16.06 82.37 1.57 5.2 49.29 6.08 44.128 0.38 0.089 0.033
Coffee waste (CW) 19.82 16.75 76.67 6.58 10.7 51.33 6.79 38.595 3.02 0.21 0.055
Mix1 (W/CW, 1:2:1/2) 19.886 15.521 81.215 3.264 8.850 50.803 6.484 41.080 1.487 0.110 0.037
Mix2 (W/DW, 1:2:1/2) 19.501 15.208 83.960 0.832 6.100 49.809 6.145 43.720 0.245 0.055 0.027
Mix3 (DW/CW, 1:2:1/2) 19.429 16.395 79.605 4.000 7.950 50.253 6.415 41.516 1.626 0.146 0.043
Mix4 (W/DW/CW, 1:3:1/3:1/3) 19.586 16.122 80.048 3.830 8.250 50.464 6.451 41.270 1.636 0.137 0.042
Glossy paper (GP) 10.4 4.5 70.7 24.8 3.8 41.9 5.3 52.587 0.1 0.02 0.093

wb: wet basis, db: dry basis, HHV: higher heating value (measured in a bomb calorimeter for the single fuels and calculated, based on the relative dry mass contribution of
each single fuel, for the fuel mixtures).

Table 2
Characteristics of the TGA experiments with the fuels.

Sample Heating rate Ar 21%O2/79%Ar

(K/min)
DTG peak DTG max Solid residue DTG peak1 DTG DTG peak2 DTG max2 Solid residue
temperature (°C) (1/s) char + ash (%) temperature (°C) max1 (1/s) temperature (°C) (1/s) Ash (%)
W 5 348.3 9.29E04 7.0 315.1 1.39E03 443.2 4.36E04 0.9
20 370.0 3.39E03 13.6 340.0 4.89E03 464.3 5.14E03 0.4
100 385.0 1.53E02 15.6 362.5 1.93E02 494.9 4.46E03 0.3
DW 5 344.3 7.86E04 7.6 312.0 1.12E03 437.8 3.35E04 2.2
20 367.4 2.93E03 18.2 333.4 4.28E03 432.5 4.57E03 1.8
100 378.2 1.28E02 18.8 350.6 1.74E02 460.3 4.89E03 1.8
CW 5 303.3 5.40E04 17.9 274.2 5.57E04 442.6 2.91E03 5.8
20 319.5 2.11E03 24.0 299.1 2.31E03 428.6 4.74E03 5.8
100 333.8 1.07E02 24.9 315.7 1.28E02 479.4 3.32E03 6.1
GP 5 340.2 9.63E04 21.4 316.5 1.26E03 416.3 2.99E04 20.4
20 362.4 3.72E03 22.4 336.5 3.26E03 449.1 3.71E03 22.8
100 367.5 1.35E02 29.3 361.1 2.41E02 440.2 6.40E03 21.6
Mix1 5 311.1/347 5.08E04/5.01E04 14.2 314.6 8.23E04 445.7 2.60E03 3.3
20 328.3/368.3 1.95E03/1.75E03 22.5 336.7 2.87E03 433.7 3.40E03 3.1
100 340.2/375.8 1.01E02/8.43E03 22.6 349.8 1.22E02 463.3 3.19E03 3.1
Mix2 5 346.9 8.35E04 11.4 313.0 1.33E03 440.5 4.21E04 1.3
20 368.4 3.09E03 17.8 337.2 5.06E03 424.7 3.98E03 1.2
100 382.1 1.38E02 18.0 358.2 1.78E02 479.8 3.70E03 1.1
Mix3 5 310.6/342.3 5.07E04/4.54E04 16.9 311.5 6.98E04 444.9 2.37E03 4.0
20 328.3/362.5 1.97E03/1.63E03 22.9 332.2 2.72E03 419.3 3.40E03 3.6
100 340.9/373.8 1.02E02/8.30E03 23.1 325.4 1.27E03 449.9 2.95E03 3.7
Mix4 5 318.5/345.3 5.03E04/5.67E04 17.6 313.4 9.39E04 437.8 5.02E04 3.2
20 340.1/366.3 1.96E03/2.19E03 21.8 336.4 3.37E03 430.2 3.34E03 2.7
100 354.9/380.8 1.01E02/1.07E02 20.9 349.1 1.36E02 482.7 2.83E03 2.5

represent 1.5 wt.% of pre-roasted green coffee), and glossy paper as
magazines. Wood pellets, demolition wood and coffee waste were
ground to fine powder, but not sieved, prior to TGA experiments,
while glossy paper was cut into approximately 2  2 mm squares
with a height of approximately 0.2 mm. In the macro-TGA experi-
ments, wood pellets were used as received (6 mm diameter pel-
lets), while demolition wood and coffee waste were pelletised to
6 mm diameter pellets. Mixtures of wood/coffee waste (Mix1) at
ratio 1/2:1/2, wood/demolition wood (Mix2) at ratio 1/2:1/2,
demolition wood/coffee waste (Mix3) at ratio 1/2:1/2 and wood/
demolition wood/coffee waste (Mix4) at ratio 1/3:1/3:1/3 were
pelletised to 6 mm diameter pellets as well for use in the macro-
TGA experiments. The moisture content, proximate and ultimate
analysis of the biomass fuels tested in TGA and macro-TGA exper-
iments are reported in Table 1.
Table 1 shows that wood, demolition wood and coffee waste
are rich in carbon (C), hydrogen (H) and oxygen (O) content, with
similar amounts of these main elements. Lv et al. [7] reported
that cellulose consists of 42.06% of C, 6.06% of H and 46.38% of
O, which is consistent with the chemical formula for cellulose
(C6H10O5)n. Coffee waste has higher ash, less volatiles and about
the same fixed carbon content compared to wood species. The
2184 A. Skreiberg et al. / Fuel 90 (2011) 2182–2197

Table 3
Parameters for the three-step devolatilization mechanism at heating rates 5 K/min, 20 K/min and 100 K/min.

Sample W DW CW GP
Heating rate 5 K/min
E1 (kJ/mol) 90.6 83.2 133.1 108.1
E2 (kJ/mol) 287.9 239.7 110.8 314.2
E3 (kJ/mol) 21.6 29.1 20 34.2
E4 (kJ/mol) – – – 476.4
log10A1 (s1) 5.53 4.88 11.06 6.93
log10A2 (s1) 22.04 18.02 7.56 24.63
log10A3 (s1) 2.05 1.55 1.90 0.871
log10A4 (s1) – – – 24.28
c1 (mg) 3.27 4.03 0.45 0.852
c2 (mg) 2.22 2.46 2.30 0.780
c3(mg) 2.03 2.24 2.24 0.757
c4(mg) – – – 0.348
fit (%) 1.15 1.67 3.36 0.91
Heating rate 20 K/min
E1 (kJ/mol) 86.5 96.4 152.2 112.0
E2 (kJ/mol) 325.0 246.7 124.4 320.6
E3 (kJ/mol) 20 20 21.8 20
E4 (kJ/mol) – – – 380.3
log10A1 (s1) 5.36 6.42 13.15 7.52
log10A2 (s1) 24.78 18.44 9.09 24.87
log10A3 (s1) 1.33 1.27 0.883 1.45
log10A4 (s1) – – – 18.56
c1 (mg) 3.31 2.68 0.64 0.711
c2 (mg) 1.33 1.96 2.86 0.599
c3(mg) 1.23 1.47 3.07 0.476
c4(mg) – – – 0.320
fit (%) 0.66 0.87 2.55 0.89
Heating rate 100 K/min
E1 (kJ/mol) 79.0 111.7 147.0 120.8
E2 (kJ/mol) 160.4 198.3 125.1 256.0
E3 (kJ/mol) 180.9 27.1 32.6 37.1
E4 (kJ/mol) – – – 278.6
log10A1 (s1) 5.84 8.43 13.11 8.94
log10A2 (s1) 12.66 14.81 9.62 19.89
log10A3 (s1) 13.31 0.219 0.815 1.13
log10A4 (s1) – – – 13.02
c1 (mg) 1.37 2.55 0.66 0.664
c2 (mg) 1.41 2.92 2.73 0.646
c3(mg) 4.63 1.82 2.79 0.474
c4(mg) – – – 0.490
fit (%) 2.39 1.06 1.77 1.18

fit (%) = Relative deviation (%).

Key data:
up to 1100 °C higher nitrogen content is due to proteins and alkaloids in coffee
ID: 195 mm, H: 2 m waste [8].
Flue gas suction system
35 + 8 + 2*4.5 = 52 kW
up to 1.2 kg fuel/h 2.2. Thermogravimetric analysis of biomass samples
up to 260 Nl air/min
Scale
Two sets of thermogravimetric experiments have been carried
Impactor out with thermobalance Mettler Toledo TGA/SDTA 8951E. The
Gas Heated filter behaviour of biomass samples under inert (argon) atmosphere
analysis was studied in the first series of thermogravimetric experiments.
FTIR,
GC,
Horiba Table 4
Platform
2 preheaters The DTG pyrolysis peak and solid residue amount from the single fuels obtained in the
Heated macro-TGA experiments at a heating rate of 5 K/min.
reactor
Sample DTG peak DTG max Solid residue
temperature (°C) (mg/s) amount (%)
View glass Rotating grate
W 404.1 151.82 23
Fuel DW 383 165.57 27
Preheater Gas bottles,
feeding
pressurised air, and CW 371.5 107.38 25
steam generator GP 376.1 97.991 28
Logging
Control

FC Mix1 380.7 175.77 25

panel Mix2 386.5 186.08 25
Ash Mix3 372.1 133.5 27
Monika II Mix4 377.1 101.54 25

Fig. 2. Schematic illustration of the macro-TGA setup. Volatiles by difference.

 A. Skreiberg et al. / Fuel 90 (2011) 2182–2197 2185

For the second series of TGA experiments with biomass samples
under oxidising atmosphere, a mixture of 21% oxygen in argon
was used. A constant flow rate of 100 ml/min was applied both
for argon and oxygen/argon (21%O2/79%Ar). Purging with argon
for 20 min, before starting the heating of the sample during pyro-
lysis TGA experiments, was carried out to be sure of an oxygen
free atmosphere. Each of the biomass samples (ffi10 ± 3 mg, ex-
cept for glossy paper: ffi2.75 ± 0.4 mg) was placed into an alumina
pan and was submitted to three different dynamic runs per-
formed at heating rates of 5, 20 and 100 K/min at temperatures
ranging from 60 to 900 °C under inert and oxidising atmosphere.
The repeatability of the TGA experiments was good, with a root
mean square value between two runs of 0.7% of the peak maxima
for the non-smoothed (based directly on the recorded TGA sam-
ple weight) dm/dt curve at a heating rate of 20 K/min in inert
atmosphere for one sample. The noise of the dm/dt curve
accounts for a significant part of this value. This uncertainty will
increase with increasing heating rate and it will decrease with
decreasing heating rate, until the noise level will at some heating
rate cause it to increase again. At combustion conditions
the uncertainty will increase further, especially for the part of
the dm/dt curve where ignition of the sample has taken place.
The characteristics of the TGA experiments for pyrolysis and
combustion of single fuels and fuel mixtures are summarised in
Table 2. Parameters for the three-step devolatilization mechanism
at heating rates 5 K/min, 20 K/min and 100 K/min are summa-
rised in Table 3.
2.3. Macro-TG experiments with biomass samples
The biomass samples investigated in the thermogravimetric
experiments were also tested in a batch reactor (macro-TGA),
shown in Fig. 2. The macro-TGA is one-of-a-kind, built by Höker
KFT (Hungary) according to design specifications from SINTEF En-
ergy Research. During macro-TGA operation the biomass fuel sam-
ples were placed in a cylindrical mesh basket connected to a
balance and lowered into the cold reactor before starting heating
of the reactor. The balance is connected to the reactor top and is
cooled with nitrogen gas to prevent overheating. The macro-TGA
experiments were performed with 200 g samples. All samples were
studied in macro-TGA experiments as pellets, without any pre-
treatment. The samples were wood, demolition wood, coffee waste
and mixtures of these biomass fuels as pellets, and pieces of glossy
paper, i.e. the same samples as studied in the TGA experiments. A

100

Wood pyrolysis
80 Demolition wood pyrolysis
Coffee waste pyrolysis
Glossy paper pyrolysis
Weight change [%]

Mix1 pyrolysis
Mix2 pyrolysis
60
Mix3 pyrolysis
Mix4 pyrolysis

40

20

0
1.2E-03

1.0E-03
Weight change derivative [1/s]

8.0E-04

6.0E-04

4.0E-04

2.0E-04

0.0E+00
0 100 200 300 400 500 600 700 800 900
Temperature [°C]

Fig. 3. TG and DTG curves for biomass fuels from pyrolysis at a heating rate of 5 K/min.
2186 A. Skreiberg et al. / Fuel 90 (2011) 2182–2197

constant flow rate of 60 Nl/min was applied for nitrogen as inert to be described by only one single kinetic differential reaction. In
atmosphere. The samples were heated at a heating rate of 5 the kinetic model of independent parallel reactions, the biomass
K/min under inert atmosphere up to 900 °C. The reactor was samples are regarded as a sum of main pseudo-components (cellu-
purged with nitrogen for at least 1 h prior to the start of the lose, hemicellulose and lignin), whose dynamics are described by
experiments. Before starting the pyrolysis experiments, an online first order kinetics [9–11]. A pseudocomponent is defined as the
oxygen analyzer was used to make sure that the reactor was free totality of those decomposing species which can be described by
from oxygen. The yield of char with ash content (solid residue) the same reaction kinetic parameters in the given model. The
and DTG pyrolysis peaks obtained from macro-TGA experiments resulting mass loss rate curve is the weighted sum of the individual
with single biomass fuels are shown in Table 4. The repeatability daj/dt reaction rates, each corresponding to decomposition of the
of the macro-TGA experiments is quite good, however, the uncer- pseudo-components [12–14]:
tainty connected to the dm/dt curve in these experiments are Ncomp
inherently significantly larger than for the TGA experiments. The dm X cj daj
 ¼ ð1Þ
released volatiles during macro-TGA experiments were cooled in dt j¼1
dt
an ice-water cooler, i.e. condensable volatiles were captured in
the cooler. The non-condensable gaseous products CO2, CO, H2 daj Ej
¼ Aj eRT ð1  aj Þ ð2Þ
and lighter hydrocarbons were analysed by a micro-GC. dt
where Aj is the pre-exponential factor (s1), Ej is the activation en-
ergy (kJ/mol), R is the gas constant (8.314 J mol1 K1), T is the tem-
3. Kinetic analysis perature (K), m is the normalised sample mass, aj is the fraction of
volatiles which escaped from pseudocomponent j until time t and
Biomass composed of fixed carbon, cellulose, hemicellulose, lig- Ncomp is the number of pseudo-components. Coefficient cj express
nin, extractives, water and mineral matter is too complex material the contribution of the partial processes to the resulting mass

100

Wood pyrolysis
80 Demolition wood pyrolysis
Coffee waste pyrolysis
Glossy paper pyrolysis
Mix1 pyrolysis
Weight change [%]

Mix2 pyrolysis
60
Mix3 pyrolysis
Mix4 pyrolysis

40

20

0
4.0E-03

3.5E-03
Weight change derivative [1/s]

3.0E-03

2.5E-03

2.0E-03

1.5E-03

1.0E-03

5.0E-04

0.0E+00
0 100 200 300 400 500 600 700 800 900
Temperature [°C]

Fig. 4. TG and DTG curves for biomass fuels from pyrolysis at a heating rate of 20 K/min.
 A. Skreiberg et al. / Fuel 90 (2011) 2182–2197 2187

loss rate and is proportional to the concentration of the jth curves that strongly depend on the experimental conditions. The
2
pseudocomponent in the sample (normalised mass of volatiles division by hk serves for normalisation [17]. The obtained fit was
formed from pseudocomponent j) [15]: characterised by the following quantity:

cj ¼ ðconcentrationÞj xðyield of v olatilesj Þ ð3Þ fitð%Þ ¼ 100S0:5 ð5Þ

The unknown kinetic parameters, the pre-exponential factors Aj

and the activation energies Ej for pyrolysis were determined by the 4. Results and discussion
method of least-squares [9,10,16]:
4.1. Thermogravimetric analysis of biomass fuels
N exp X
X Nk
½ðdm Þobs ðt i Þ  ðdm
dt k
Þcalc ðt i Þ2
dt k 4.1.1. Pyrolysis experiments
S¼ 2
ð4Þ
k¼1 i¼1 N k hk The thermogravimetric (TG) and derivative thermogravimetric
(DTG) curves for biomass fuels obtained from pyrolysis experi-
The experiments on a given sample were evaluated simulta- ments at different constant heating rates of 5, 20 and 100 K/min
neously by comparing the normalised mass loss rate (dm/dt)obs, are shown in Figs. 3–5.
to their simulated counterparts, (dm/dt)calc. Subscript k indicates It was observed that pyrolysis of single biomass fuels and bio-
the different experiments, Nexp is the number of experiments eval- mass mixtures occur in a single stage, glossy paper excepted. In
uated simultaneously, ti denotes the time values in which the dig- case of glossy paper, a second stage was observed caused by
itized (dm/dt)obs values were taken, Nk is number of the ti points in CaCO3 to CaO and CO2 conversion [18,19]. Calcium carbonate
a given experiment and hk denotes the heights of the evaluated (CaCO3) is nowadays commonly used as an additive to make

100

Wood pyrolysis
80 Demolition wood pyrolysis
Coffee waste pyrolysis
Glossy paper pyrolysis
Weight change [%]

Mix1 pyrolysis
Mix2 pyrolysis
60
Mix3 pyrolysis
Mix4 pyrolysis

40

20

0
1.8E-02

1.6E-02
Weight change derivative [1/s]

1.4E-02

1.2E-02

1.0E-02

8.0E-03

6.0E-03

4.0E-03

2.0E-03

0.0E+00
0 100 200 300 400 500 600 700 800 900
Temperature [°C]

Fig. 5. TG and DTG curves for biomass fuels from pyrolysis at a heating rate of 100 K/min.
2188 A. Skreiberg et al. / Fuel 90 (2011) 2182–2197

100

80
5 K/min pyrolysis
20 K/min pyrolysis

Weight change [%]

100 K/min pyrolysis
60

40

20

0
1.4E-02

1.2E-02
Weight change derivative [1/s]

1.0E-02

8.0E-03

6.0E-03

4.0E-03

2.0E-03

0.0E+00
0 100 200 300 400 500 600 700 800 900
Temperature [°C]

Fig. 6. TG and DTG curves for demolition wood at different heating rates of 5, 20, 100 K/min under inert atmosphere.

the paper glossy [20]. At temperatures lower than about 100 °C, a DTG curves for demolition wood at the different heating rates
small weight change of the samples is attributed to moisture of 5, 20 and 100 K/min. The deviation for the 5 K/min curve is
evaporation. The DTG curves at different heating rates of 5, 20 probably due to char decomposition caused by a small air leak-
and 100 K/min indicate similar qualitative results. First, the coffee age. Comparing the char yield obtained from the TGA experi-
waste starts to decompose at a temperature slightly below 200 °C, ments with the combined fixed C and ash yield obtained from
followed by wood and demolition wood. Glossy paper started to the proximate analysis of the fuels (Table 1), it can be seen that
release volatiles at a temperature of about 250 °C. The fuel mix- the average char yield at a heating rate of 5 K/min is about 70%
tures decomposition resembles the mixtures single fuels contri- of the proximate analysis value, at 20 K/min it increases to
bution. From the DTG curves for the single biomass fuels a 104% and with a further increase to 109% at 100 K/min. This illus-
hemicellulose shoulder can be seen at the low temperature side trates clearly the influence of heating rate on the final char yield.
and a DTG peak associated with cellulose pyrolysis. Above a tem- A comparison of the thermal behaviour of fuel mixtures with
perature of 400 °C weight losses are still seen in the DTG curves. single fuels during pyrolysis at a heating rate of 5 K/min is shown
This corresponds to the slow lignin decomposition process that in Fig. 7.
occurs in a wide temperature range. The DTG peaks from the sin- From the comparison of single fuels with fuel mixtures at a con-
gle fuels are also clearly visible for the mixtures, at close to iden- stant heating rate of 5 K/min it can be seen that two fuels pyroly-
tical temperatures as observed in the single fuels experiments. sed together clearly displays a contribution from the two
However, at the highest heating rate of 100 K/min these single individual decomposition behaviours in the TGA experiments.
peaks become less distinct/visible. The TG curves move to higher Fig. 8 compares DTG curves of biomass fuels obtained in com-
temperatures with increasing heating rate and DTG peak temper- bustion TGA experiments with those obtained under inert condi-
ature increases with heating rate from 344.3 °C to 378.2 °C as tions in a temperature range from 60 to 900 °C at a constant
shown in Fig. 6 for demolition wood. Fig. 6 shows the TG and heating rate of 5 K/min. The DTG peaks temperatures and rates
 A. Skreiberg et al. / Fuel 90 (2011) 2182–2197 2189

are reported in Table 2. Comparing the reactivities (DTG peak
rates) for the different fuels it can be seen that at a heating rate
of 5 K/min glossy paper has the highest reactivity, followed by
wood, demolition wood and coffee waste. This is also the case at
20 K/min, but at 100 K/min wood and glossy paper change place,
with wood having the highest reactivity.
4.1.2. Combustion experiments
Two stages were distinguished in the DTG curves determined
from the combustion TGA experiments. The first stage in the
range of 200–370 °C is caused by the combination of total decom-
position of hemicellulose and cellulose and partial decomposition
of lignin, and the second one in the range of 370–490 °C corre-
sponding to the decomposition of the remaining lignin and char
oxidation, leaving behind only residual ash. For coffee waste
and the two mixtures with 50% coffee waste high DTG peaks
are seen during char oxidation. This can be explained by higher
char reactivity of the coffee waste char, which may also cause dis-
turbances in the TGA weight measurements, resulting in too high
DTG peaks. However, this effect could not be seen for the mixture
with only one-third coffee waste. The process of thermal decom-
position under oxidative atmosphere occurs earlier than at pyro-
lysis conditions and the DTG pyrolysis peaks obtained during
combustion TGA experiments are higher and shift towards lower
temperatures (Table 2). For the DTG curve of glossy paper ob-
tained under oxidative atmosphere three peaks are observed.
The first two occurs at temperatures of 316.5 °C and 416.3 °C
and are followed by a peak at 645.4 °C, caused by CaCO3 to CaO
and CO2 conversion. Weight loss relative to the first two stages
is approximately 70%, and there was 20.4% of solid residue left
at 900 °C. Presence of oxygen enhances the decomposition at a
certain temperature where the oxygen will cause ignition of the
volatiles, and when the temperature is high enough oxygen pro-
motes the heterogeneous oxidation of the remaining char. From
the single fuels DTG data the DTG behaviour of the fuel mixtures
was simulated, showing in general good correspondence, but with
decreasing correspondence with increasing heating rate. The cof-
fee waste started to release volatile compounds below 200 °C,

Observations Calculated
Observations-From single fuels Calculated-From single fuels
1.E-02
Mix1 Mix2

9.E-03
Weight change derivative [mg/s]

8.E-03

7.E-03

6.E-03

5.E-03

4.E-03

3.E-03

2.E-03

1.E-03

0.E+00
1.E-02
Mix3 Mix4

9.E-03
Weight change derivative [mg/s]

8.E-03

7.E-03

6.E-03

5.E-03

4.E-03

3.E-03

2.E-03

1.E-03

0.E+00
0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature [°C] Temperature [°C]

Fig. 7. Comparison of the observed and calculated pyrolysis DTG curves for the fuel mixtures at a heating rate of 5 K/min.
2190 A. Skreiberg et al. / Fuel 90 (2011) 2182–2197

3.0.E-03
Wood Demolition wood
Weight change derivative [1/s]

2.5.E-03
Pyrolysis
Combustion
2.0.E-03

1.5.E-03

1.0.E-03

5.0.E-04

0.0.E+00
3.0E-03
Coffee waste Glossy paper
Weight change derivative [1/s]

2.5E-03

2.0E-03

1.5E-03

1.0E-03

5.0E-04

0.0E+00
3.0E-03
Mix1 Mix2
Weight change derivative [1/s]

2.5E-03

2.0E-03

1.5E-03

1.0E-03

5.0E-04

0.0E+00
Weight change derivative [1/s]

3.0E-03
Mix3 Mix4

2.5E-03

2.0E-03

1.5E-03

1.0E-03

5.0E-04

0.0E+00
0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature [°C] Temperature [°C]

Fig. 8. Comparison of pyrolysis and combustion DTG curves for biomass fuels at a heating rate of 5 K/min.

wood and demolition wood at somewhat above 200 °C followed curve from hemicellulose at combustion conditions may be dis-
by glossy paper at about 250 °C. A typical shoulder peak was guised by the influence of the exothermal volatiles combustion
not observed in the first stage of the DTG curves determined un- on the sample. When oxygen presents, the thermal reactivity of
der oxidative atmosphere. The individual contribution to the DTG biomass (especially the cellulose) is greatly enhanced due to the
 A. Skreiberg et al. / Fuel 90 (2011) 2182–2197 2191

9.0E-03
Observations Calculated 1st 2nd 3rd

Weight change derivative [mg/s]

8.0E-03
5 K/min
7.0E-03
fit: 1.67%
6.0E-03

5.0E-03

4.0E-03

3.0E-03

2.0E-03

1.0E-03

0.0E+00

2.5E-02
Weight change derivative [mg/s]

20 K/min

2.0E-02

fit: 0.87%

1.5E-02

1.0E-02

5.0E-03

0.0E+00

1.4E-01
Weight change derivative [mg/s]

1.2E-01
100 K/min
1.0E-01
fit: 1.06%
8.0E-02

6.0E-02

4.0E-02

2.0E-02

0.0E+00
0 100 200 300 400 500 600 700 800 900 1000
Temperature [°C]

Fig. 9. Comparison between observed and simulated DTG curves for demolition wood heated at 5, 20 and 100 K/min, by means of a three-step devolatilisation mechanism.
Colour lines denote the predicted volatiles evolution from the different pseudo-components. (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

acceleration of mass loss in the first stage, and complex reactions
occur simultaneously in the second stage when char and lignin
oxidise [21].
4.2. Three-step devolatilisation mechanism of single biomass fuels
A three-step devolatilisation mechanism with dependence on
species concentrations, for the volatile fractions of the pseudo-
components hemicellulose, cellulose and lignin, was applied to
describe the dynamic thermogravimetric curves of the single fuels.
Cellulose, hemicellulose and lignin cover 40–60, 20–40, and
10–25 wt.% of biomass materials on dry basis, respectively. The ratio
of the three components in a biomass differs with the source of the
biomass [22,23]. Previous studies [9,11,13,23,24] showed that it is
important to distinguish the behaviour of the three components
for a better understanding of the biomass pyrolysis process. The
DTG curves of the three pseudo-components for demolition wood
at different heating rates of 5, 20 and 100 K/min are shown in Fig. 9.
Modelling showed that at all heating rates (5, 20 and 100
K/min), after moisture evolution, demolition wood decomposes
2192
1.E-02
9.E-03
Weight change derivative [mg/s]
8.E-03
7.E-03
6.E-03
5.E-03
4.E-03
3.E-03
2.E-03
1.E-03
0.E+00
200
Fig. 10. Comparison between observed and simulated DTG curves for Mix2 at 5 K/min, by means of a combined three-step devolatilisation mechanism. Colour lines denote
the predicted volatiles evolution from the different wood and demolition wood pseudo-components. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
in stages of hemicellulose and cellulose, independent of each
other, and lignin at a slower rate. The pyrolysis of hemicellulose
started at a temperature above 200 °C and the cellulose started
to decompose at a temperature above 300 °C, i.e. close to the
DTG pyrolysis peak of hemicellulose. In comparison to the sharper
DTG peaks of cellulose and hemicellulose, lignin has wide and flat
DTG peaks. Lignin started to decompose at about the same tem-
perature as hemicellulose and showed gradual weight loss until
900 °C. The calculated activation energies for demolition wood,
shown in Table 3, varied depending on heating rate between
83.2 and 111.7 kJ/mol for hemicellulose, 198.3–246.7 kJ/mol for
cellulose and 20–29.1 kJ/mol for lignin at all heating rates for
demolition wood and are in good agreement with activation ener-
gies for woody biomass published by Di Blasi [24] and Grønli [25].
The lower activation energies of hemicellulose in thermal decom-
position are attributed to its chemical structure. Hemicellulose has
a random amorphous structure with little strength. The cellulose
molecule is a very long polymer of glucose units without any
branches, and it is crystalline, i.e. strong. Lignin is different from
cellulose and hemicellulose, which are composed of polysaccha-
rides, since it is composed of three kinds of benzene–propane
structures and which are heavily cross-linked. The thermal stabil-
ity of lignin is thus very variable, and it decomposes over a wide
temperature range and is more difficult to decompose completely
than hemicellulose and cellulose, i.e. also higher temperatures are
needed [22,23,26].
The three-step devolatilisation mechanism was applied to de-
scribe also the DTG curves for biomass mixtures. The three-step
mechanism is used separately for the fuels in the mixtures and
then summed according to the single fuels fraction in the mixtures.
As an example the contribution from both three-step devolatilisa-
tion mechanisms of the single fuels at a heating rate of 5 K/min is
shown in Fig. 10 for Mix2, wood/demolition wood prepared at ratio
1/2:1/2.
The hemicelluloses, celluloses and lignins partial curves of
demolition wood and wood are very close to each other, which is
due to close values of activation energies of the three main pseu-
do-components of the wood and the demolition wood samples.
A. Skreiberg et al. / Fuel 90 (2011) 2182–2197
Observations Calculated 1st-W 2nd-W
3rd-W 1st-DW 2nd-DW 3rd-DW
250 300 350 400 450
Temperature [°C]
4.3. Macro-TGA experiments with biomass fuel samples
From Table 4 follows that pyrolysis of single biomass fuels in
the macro-TGA occurs at the lowest temperature in the case of cof-
fee waste (DTG peak at 371.5 °C), followed by glossy paper
(376.1 °C), demolition wood (383 °C) and wood (404.1 °C). Solid
residues (char with ash content) in range 23–28 wt.% were gener-
ated at the end of the pyrolysis process during macro-TGA experi-
ments. The thermogravimetric analysis of the fuels in comparison
with macro-TGA experiments, both performed under inert atmo-
sphere at a heating rate 5 K/min, are reported in Fig. 11.
From the figure follows that in the TGA, the pyrolysis of e.g.
wood occurs faster than in the macro-TGA with the weight loss
mainly in the temperature range 200–350 °C compared to 300–
450 °C in the macro-TGA. The heat and mass transfer limitations
of the larger samples used in the macro-TGA cause a lag in the tem-
perature evolution of these samples compared to the much smaller
TGA samples. The solid residue, char with ash content, in the TGA
experiment was 7% while the macro-TGA solid residue was 23%.
The higher char yield from the larger samples used in the macro-
TGA is most likely due to increased secondary char forming reac-
tions. An influence of the sample size in the TGA on the char yield
was not found, however, a clear and consistent influence of the
heating rate was found. Also the reactivity order changes in the
macro-TGA experiments, with demolition wood having the highest
reactivity, followed by wood, coffee waste and glossy paper. Again,
heat and mass transfer limitations are the likely reason, for the
changed order.
A comparison of the thermal behaviour of fuel mixtures with
single fuels during pyrolysis at a heating rate of 5 K/min is shown
in Fig. 12. From the comparison of single fuels with fuel mixtures at
a constant heating rate of 5 K/min it can be seen that two fuels pyr-
olysed together qualitatively and to some extent quantitatively
displays a contribution from the two individual decomposition
behaviours in the TGA experiments, but clearly heat and mass
transfer limitations of the individual fuels cannot be directly
extrapolated to the fuel mixtures. The condensable and non-
condensable gaseous products formed during macro-TGA
 A. Skreiberg et al. / Fuel 90 (2011) 2182–2197 2193

1.E-03 TGA Macro-TGA

Weight change derivative [1/s]
9.E-04
Wood Demolition wood
8.E-04

7.E-04
6.E-04
5.E-04

4.E-04
3.E-04
2.E-04

1.E-04
0.E+00
1.E-03
Glossy paper
Weight change derivative [1/s]

Coffee waste
9.E-04

8.E-04
7.E-04

6.E-04
5.E-04
4.E-04

3.E-04
2.E-04
1.E-04

0.E+00
1.E-03
Mix2
Weight change derivative [1/s]

Mix1
9.E-04

8.E-04
7.E-04
6.E-04
5.E-04
4.E-04
3.E-04

2.E-04
1.E-04
0.E+00
Weight change derivative [1/s]

1.E-03
Mix3 Mix4
9.E-04
8.E-04
7.E-04
6.E-04
5.E-04
4.E-04
3.E-04
2.E-04
1.E-04
0.E+00
0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature [°C] Temperature [°C]

Fig. 11. The DTG curves of biomass fuels determined from TGA and macro-TGA experiments, both performed under inert atmosphere at a heating rate of 5 K/min.

experiments with biomass samples can be the results of biomass macro-TGA experiments at a heating rate of 5 K/min as a function
components decomposition as well as results of further reactions of temperature is shown in Fig. 13.
of volatiles formed during thermal decomposition of biomass Typical gases, such as CO2, CO, H2 and some light hydrocarbons
samples. The composition of the dry gas generated during the (CH4, C2H6, C2H2 and C2H4) were identified in the non-condensable
2194 A. Skreiberg et al. / Fuel 90 (2011) 2182–2197

Observations Observations-From single fuels

2.0E+02
Mix1 Mix2
1.8E+02

1.6E+02
Weight change derivative [mg/s]

1.4E+02

1.2E+02

1.0E+02

8.0E+01

6.0E+01

4.0E+01

2.0E+01

0.0E+00
2.0E+02
Mix3 Mix4
1.8E+02

1.6E+02
Weight change derivative [mg/s]

1.4E+02

1.2E+02

1.0E+02

8.0E+01

6.0E+01

4.0E+01

2.0E+01

0.0E+00
0 100 200 300 400 500 600 700 0 100 200 300 400 500 600 700
Temperature (°C) Temperature (°C)

Fig. 12. Comparison of the observed and calculated pyrolysis DTG curves in the macro-TGA for the fuel mixtures at a heating rate of 5 K/min.

gaseous products generated during the macro-TGA experiments.
Water vapour was also released during the experiments, but it
could not be detected by the micro-GC. Also other gas species
are formed, e.g. several authors [27–29] report that during thermal
decomposition of nitrogen containing materials, fuel-nitrogen is
converted to ammonia (NH3), isocyanic acid (HNCO), hydrogen
cyanide (HCN) and organic nitrogen. The main dry gas components
released from all samples were CO and CO2. The concentration of
CO and CO2 passed through a maximum in the temperature range
350–400 °C and decreased with increasing temperature. In case of
glossy paper a second high peak of CO2 was observed at a temper-
ature above 600 °C caused by CaCO3 thermal decomposition. Sig-
nificant amounts of hydrogen were detected at temperatures
higher than 500 °C. Compared with other gas species, the release
of light hydrocarbons (CH4, C2H6, C2H2 and C2H4) was generally
low. It was observed using as example demolition wood (Fig. 9)
that hemicellulose and cellulose contribute to high CO2 and CO
yields. Lignin forms more hydrogen and methane. When the deg-
radation of hemicellulose and cellulose is complete at a tempera-
ture of about 400 °C, CO2 together with H2O can be produced by
lignin degradation, through release of COOH groups or rupture of
C–O groups [22,30]. The gases released from biomass fuels mix-
tures demonstrated that the composition of gases qualitatively fol-
lows from the individual behaviour of the single fuels. This was
especially the case for the 1/2DW:1/2CW mixture (Mix3), as
shown in Fig. 14 and which is consistent with Fig. 12. However,
in case of the last experiment, with Mix4 (1/3 W:1/3DW:1/3CW),
the CO2 content was significantly lower, due to tar species contam-
ination of the specific column measuring CO2, and C2H2, C2H4 and
C2H6.
5. Conclusions
The thermal behaviour of single biomass fuels and selected fuel
mixtures were investigated using TGA and macro-TGA pyrolysis
characteristic connected with micro-GC for gas monitoring. In
addition, combustion TGA experiments were performed with the
same fuels. Thermogravimetric analysis showed that each single
 A. Skreiberg et al. / Fuel 90 (2011) 2182–2197 2195

1.8
Wood Demolition wood
Quantity/H2
1.6
Quantity/CH4
1.4 Quantity/CO
Quantity/CO2
1.2 Quantity/C2H2 + C2H4
Vol%

Quantity/C2H6
1

0.8

0.6

0.4

0.2

0
2

1.8
Glossy paper
Coffee waste
1.6

1.4

1.2
Vol%

0.8

0.6

0.4

0.2

0
2

1.8
Mix1 Mix2
1.6

1.4

1.2
Vol%

0.8

0.6

0.4

0.2

0
2
1.8
Mix3 Mix4
1.6
1.4
1.2
Vol%

1
0.8
0.6
0.4
0.2
0
0 200 400 600 800 0 200 400 600 800
Temperature [°C] Temperature [°C]

Fig. 13. Composition of the dry gas generated during macro-TGA experiments with biomass fuels at a heating rate of 5 K/min.

fuel had pyrolysis and combustion characteristic based on its own tures and the gas composition analysis from macro-TGA experi-
main pseudo-components (hemicellulose, cellulose and lignin). ments showed respectively quantitative and qualitative
The pyrolysis and combustion characteristics of selected fuel mix- summative behaviour based on the single fuels. A kinetic model
2196 A. Skreiberg et al. / Fuel 90 (2011) 2182–2197

1.2 1.4

CW DW Mix3

1.2
1
CO CO2

1
0.8

0.8
Vol%

0.6

0.6

0.4
0.4

0.2
0.2

0 0
0.35 0.7

0.3 0.6

CH4 H2
0.25 0.5

0.2 0.4
Vol%

0.15 0.3

0.1 0.2

0.05 0.1

0 0
0 200 400 600 800 0 100 200 300 400 500 600 700 800 900
Temperature [°C] Temperature [°C]

Fig. 14. Comparison of the dry gas generated during macro-TGA experiments for DW, CW and 1/2DW:1/2CW (Mix3) at a heating rate of 5 K/min.

of independent parallel reactions was applied to the experimental
results of TGA pyrolysis at a heating rate of 5 K/min using a three-
step devolatilisation mechanism in case of single fuels and fuel
mixtures. The gases released during macro-TGA experiments were
major components as CO2, CO, H2 and some light hydrocarbons
(CH4, C2H6, C2H2 and C2H4).
Acknowledgements
This work was carried out within the competence building pro-
ject KRAV, funded by the Research Council of Norway, five Norwe-
gian Industry Partners and SINTEF Energy Research. Dr. Gabor
Varhegyi is acknowledged for making his software, used in deter-
mination of DTG curves and in kinetic calculations, available.
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